Water-soluble anthraquinone dyestuffs and process for making same



sulph-(alkyl) -amides.

Patented Jan. 8, 1935 UNITED STATES PATENT OFFICE WATER- SOLUBLEANTHBAQUINONE DYE- STUFFS SAME AND PROCESS FOR MAKING Albin Peter,Basel, Switzerland, assignor to firm Chemical Works formerly Sandoz,Basel,

Switzerland No Drawing. Application January 31, 1934, Serial No.709,236. In Switzerland February 8, 1933 90laims.

It has been found, that new, water-soluble anthraquinone dyestuffs canbe prepared by condensing l-amino-2-sulpho-4-halogen anthraquinones with4-amino-1-methylbenzene-2- As alkylamides the monoand dimethyl ormonoand diethyl derivatives may be used. In order to carry out thepresent invention, the starting compounds are heated in an aqueoussolution or suspension and in presence of acid binding agents and ofcatalyzers, until the condensationhas completely occurred.

As acid binding agents compounds such as sodium bicarbonate andpotassium bicarbonate may be used. As catalyzers those generally used inthe synthesis of anthraquinone compounds, like copper and coppercompounds may be employed.

The condensation may be carried out in an open or closed vessel andeventually under pres- OIM sure and at temperatures of 50-l50 0.,whereby I temperatures of fill-90 C. are preferably used.

It is further preferable to use for the condensation equimolecularquantities of the starting compounds, but an excess of one of thecomponents can also be employed, and it may be advantageous to work in acarbon dioxide atmosphere, in order to refrain the dissociation of theacid binding agent.

The'end of the condensation is indicated by the fact thatthe reactionmixture does not become bluer.

The products obtained by the present process are isolated from thereaction mixture by pouring same into acidified water or an aqueoussolu- -tion of a salt, separating the precipitate by filtration,dissolving it in water and salting it out from its solution.

The dyestufl's obtained in this manner possess 40 the following generalformula: j

COM

0 B NHQCH: Or-A W wherein A represents an alkylated amino group and Mrepresents an alkali metal. They dye animal fibres blue shade ofexcellent fastness to milling, washin perspiration and light.

One object of the present invention is a process 0 w A NHQCH;

wherein A represents an alkylated amino group and M represents an alkalimetal, which dyestuffs dye animal flbres fast blue shades.

The following examples, without being limitative, show the manner inwhich the process can be carried out, the parts being by weight:-

Example 1 A mixture consisting of 15 parts of the sodium salt of1-amino-4-bromoanthraquinone-2-sulphonic acid, of 12 parts of4-amino-1-methylbenzene-2-sulph-dimethylamide, of 4.5 parts of sodiumbicarbonate, of 0.3 part of cuprochloride and of 150 parts of water isstirred at 90-95" C. during 3-4 hours in a carbon dioxide atmosphere ina vessel provided with a reflux condenser.

The reaction mixture is then poured into a diluted aqueous solution ofsodium chloride, the precipitate is filtered off, dissolved in water,separated by filtration from the copper salts and salted out.

In dry state the dyestuflf is a dark-blue powder, soluble in water witha pure blue coloration. In concentrated sulphuric acid it'yields aweakly colored greenish blue solution, which on addition ofparaformaldehyde becomes strongly colored in an emerald green shade.

The dyestuff dyes wool and silk from an acid bath pure blue shades ofexcellent fastness to milling, washing, perspiration and light.

The formula of the dyestufi is:

Example 2 A mixture consisting of 12 parts of 4-amin0-1-methylbenzene-2-su1ph-mono (methyl) amide, of 15 parts of1-amino-2-sulpho-4-bromoanthraquinone, of 15 parts of sodiumbicarbonate, of 1 part of copper powder and of 400 parts of water isstirred in a carbon dioxide atmosphere during 16 hours at 60 C. Thedyestuif thereby obtained is filtered, dissolved in water, filteredagain, and salted out. 1

In dry state the dyestuff thus obtained is a dark blue powder, solublein water with a pure blue coloration. In sulphuric acid it gives a dullblue solution which in presence of boric acid and on heating becomescolored in a green-blue shade; on addition of formaldehyde, thesulphuric acid solution becomes emerald green.

The dyestufi dyes wool and silk from an acid bath a pure blue shade ofvery good fastness to milling, washing, perspiration and light.

By using the respective quantities of l-amino-2-sulpho-4-chloroanthraquinone instead of the bromo-derivative, the samedyestuff will be obtained.

The formula of the dyestuff is E NH,

OaM

"What I claim is:

1. A process for the manufacture of watersoluble dyestuffs of the,anthraquinone series, consisting in heating a 1-amino-2-sulpho-4-halogenathraquinone with a 4-amino-1-methylbenzene-2-sulph-(alkyl) amidein presence of acid binding agents.

2. A process for the manufacture of watersoluble dyestufis of theanthraquinone series, consisting in heating a 1-amino-2-sulpho-4-halogenanthraquinone with a 4-amino-1-methylbenzene-2-sulph- (alkyl)amide in an aqueous medium and in presence of acid binding agents.

3. A process for the manufacture of watersoluble dyestuffs of theanthraquinone series, consisting in heating a 1-amino-2-sulpho-4-halogenanthraquinone with a 4-amino-1-methylbenzene-2-sulph-(alky1)amidein an aqueous medium in presence of acid binding agents and of coppersalts.

4. A process for the manufacture of watersoluble dyestufis of theanthraquinone series, consisting in heating a 1-amino-2-sulpho-4ehalogenanthraquinone with a 4-amino-1-methylbenzene-2-sulph-(alkyl)amide in an aqueous medium and in a carbon dioxide atmosphere, inpresence of acid binding agents and of copper salts.

5. A process for the manufacture of a watersoluble dyestuff of theanthraquincne series, consisting in heating up to 6090 C. l-amino-2-sulpho-4-bromo-anthraquinone with 4-aminol-methylbenzene-Z -sulph-('monomethyl) amide in an aqueous medium and .in a carbon dioxideatmosphere, in presence of sodium bicarbonate and copper salts.

6. A process for the manufacture of a watersoluble dyestufi of theanthraquinone series, consisting in heating up to 60-90 C. l-amino-Z-sulpho-4-bromoanthraquinone with 4-amino-1-methylbenzene-z-sulph(dimethyl) -amide in an aqueous medium and in a.carbon dioxide atmosphere, in presence of sodium bicarbonate and coppersalts.

'7. The water-soluble blue dyestuifs of the general formula:

E NH:

8. The water-soluble blue dyestufi' of the 101? mula:

E NH:

0 3 NE on,

OPNH. cm

wherein M represents an alkali metal, said dyestufi being in dry statea. dark-blue powder, solu ble in water with a blue coloration andyielding in sulphuric acid a dull-blue solution, that on addition offormaldehyde becomes emeraldgreen, and dyeing wool and silk fast blueshades.

9. The water-soluble blue dyestufl of the formula:

NH CH:

wherein M represents an alkali metal, said dyestufi being in dry state adark-blue powder, soluble in water with a blue coloration and yieldingin sulphuric acid a greenish-blue solution, that on addition offormaldehyde becomes emerald-green, and dyeing wool and silk fast blueshades.

All-BIN PETER.

